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Updated: Feb 17, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Electron and excitation energy transfers in covalently linked donor-acceptor dyads: mechanisms and dynamics revealed
Lorenzo Cupellini1, Samuele Giannini, Benedetta Mennucci
1Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Moruzzi 3, 56124 Pisa, Italy. Benedetta.Mennucci@unipi.it lorenzo.cupellini@for.unipi.it.
Abstract:
Photoinduced electron transfer (ET), hole transfer (HT), charge recombination (CR) and energy transfer (EET) are fundamental mechanisms, which occur in both natural and artificial light harvesting systems. Here, we present a computational strategy which determines ET, HT, CR and EET rates in a consistent way and merges them in a kinetic model to reproduce the net excited state dynamics. The effects of the solvent are included in all steps of the calculations making the present strategy a useful tool for a rational design of charge and energy transfer processes in complex systems. An application to covalently linked zinc and free-base porphyrin-naphthalenediimide dyads is presented. For each of the two systems, ultrafast optical spectroscopy experiments have shown a specific photophysics with different processes taking place simultaneously. The model reveals that such a diversity is mainly due to the different relative stability of the charge-separated state, while the electronic couplings for charge and energy transfer processes are quite similar in the two dyads.
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